This invention relates to novel azo dyes use as dyes, as an ingredient of an ink-jet printing ink and also substrates dyed with such compounds.
This invention relates to novel azo dyes of the formula (I) 
where the substituents are each as defined below, their preparation, their use as dyes and as an ingredient of an ink-jet printing ink and also substrates dyed with such compounds.
This invention relates to novel azo dyes of the formula (I) 
where
R1 and R2 are independently H or xe2x80x94SO3H,
X is a halogen atom, especially F or Cl,
Y is an alkali-detachable group, especially xe2x80x94OSO3H, Cl, Br, xe2x80x94OPO3H2, xe2x80x94SSO3H, xe2x80x94OCOCH3, xe2x80x94OCOC6H5 or xe2x80x94OSO2CH3 
R3 is xe2x80x94NR4R5, where R4 and R5 are independently hydrogen, a linear or branched C1-10-alkyl group which may additionally be interrupted by one or more identical or different heteroatoms or functional groups, especially by xe2x80x94Oxe2x80x94 and/or xe2x80x94SO2xe2x80x94, and which may optionally be substituted; a phenyl group, which may optionally be substituted by one or more identical or different radicals, especially by C1-4-alkyl, preferably xe2x80x94CH3, xe2x80x94SO3H or xe2x80x94SO2xe2x80x94CH2CH2xe2x80x94Y, where Y is as defined above, or R4 and R5 may combine with the nitrogen to which they are bonded to form a C3-C8 ring which may additionally contain one or more identical or different heteroatoms, especially O, S or N, preferably additionally an N or an O,
subject to the proviso that when R4 or R5 is an xe2x80x94SO2CH2CH2OSO3H-substituted phenyl group, R1 is always xe2x80x94SO3H,
or R3 has the formula (Ia) 
where
X, Y, R1 and R2 are each as defined in the formula (I),
R6 and R6xe2x80x2 are independently H or a linear or branched C1-6-alkyl group, preferably a linear C1-4-alkyl group, and B is a phenylene group or a linear or branched C1-10-alkylene group, which may optionally be substituted,
subject to the proviso that the position of the xe2x80x94NHxe2x80x94 group on the naphthyl ring and the position of the xe2x80x94SO2(CH2)2xe2x80x94Y group on the phenyl ring are identical to those of the formula (I),
and also mixtures thereof and their salts.
Useful cations for salt formation include in particular alkali metal or alkaline earth metal cations.
In preferred compounds of the formula (I), R3 is xe2x80x94NR4R5, where R4 and R5 are independently H, unsubstituted or HOxe2x80x94, HOOCxe2x80x94, HO3Sxe2x80x94, HO3SOxe2x80x94 or halogen-substituted xe2x80x94CH3 and xe2x80x94CH2CH3, linear C4-6-alkyl groups which are interrupted by xe2x80x94Oxe2x80x94 and/or SO2xe2x80x94 and which are additionally substituted by Y having the abovementioned meanings, preferably Cl or xe2x80x94OSO3H; or monosubstituted phenyl groups, substituted in particular by xe2x80x94CH3, xe2x80x94SO3H or xe2x80x94SO2CH2CH2Y, where Y is as defined above, preferably xe2x80x94OSO3H, although in the latter case the abovementioned proviso again applies that R1 is always xe2x80x94SO3H.
In likewise preferred compounds of the formula (I), R3 has the formula (Ia) where
R6 and R6xe2x80x2 are independently H, xe2x80x94CH3 or xe2x80x94CH2CH3,
B is a linear or branched C2-6-alkylene group or a phenylene group and
X is F.
In particularly preferred compounds of the formula (I), R3 is xe2x80x94NR4R5, where NR4R5 is
NHCH3, xe2x80x94NHCH2CH3, xe2x80x94N(CH3)2, xe2x80x94N(CH2CH3)2, xe2x80x94NHCH2COOH, xe2x80x94NHCH2CH2OH,
NHCH2CH2SO3H, xe2x80x94NHCH2CH2OSO3H, xe2x80x94N(CH3)CH2CH2OH,
NHCH2CH2SO2CH2CH2OSO3H, xe2x80x94NHCH2CH2CH2SO2CH2CH2OSO3H,
NHCH2CH2OCH2CH2SO2CH2CH2Cl, 
xe2x80x83and Y is xe2x80x94OSO3H.
In particularly preferred compounds of the formula I, R3 has the formula (Ia) where R6 and R6xe2x80x2 are hydrogen, B is xe2x80x94CH2CH2xe2x80x94, xe2x80x94CH(CH3)CH2xe2x80x94, xe2x80x94abd T us xe2x80x94OSO3H. 
and Y is xe2x80x94OSO3H.
In a likewise particularly preferred compound of the formula (I), R3 has the formula (Ia) where R6 is xe2x80x94CH3 and R6xe2x80x2 is H, while B is xe2x80x94CH2CH2xe2x80x94 and Y is xe2x80x94OSO3H.
A likewise particularly preferred compound has the formula (Ib) 
where R5 is H or a substituted or unsubstituted C1-4-alkyl group and X is Cl or F.
A further aspect of the present invention is the synthesis of the compounds according to the invention, which comprises coupling a compound of the formula 
with the diazo compound of an amine of the formula (III) 
where the substituents in the formula (II) and the substituents in the formula (III) are each as defined above, under generally known conditions.
This coupling takes place at a pH of 5-8, preferably 6-7. The reaction temperature is between 0 and 40xc2x0 C., preferably between 10 and 30xc2x0 C., particularly preferably between 20 and 30xc2x0 C. The compounds according to the invention are isolated and aftertreated according to known methods.
The compounds of the formula (I) and mixtures thereof and their salts are reactive dyes; they are useful for dyeing or printing hydroxyl-containing or nitrogenous organic substrates.
Another aspect of the invention is accordingly a process for dyeing or printing hydroxyl-containing or nitrogenous organic substrates, which comprises dyeing or printing with the above-defined compounds, their salts or mixtures.
Preferred substrates are leather and fiber materials comprising natural or synthetic polyamides and especially natural or regenerated cellulose, such as cotton, filament viscose or staple viscose. The most preferred substrate is textile material comprising cotton.
Another aspect of the present invention is the use of the above-defined compounds, their salts or mixtures for dyeing or printing the above-described substrates.
The compounds of the formula (I) can be used in dyeing liquors or in print pastes according to all dyeing or printing methods customary for reactive dyes.
Preferably they are dyed up by the exhaust method in the temperature range of 40 to 100xc2x0 C.
The compounds of the invention can be used as individual dyes or else, because of their excellent compatibility, as combination elements with other reactive dyes of the same class possessing comparable dyeing properties, for example their general fastnesses, their exhaustion and fixation value, etc. The combination dyeings obtained have similar fastnesses to the dyeings with the individual dye.
The compounds of the formula (I) provide good exhaustion and fixation values. The unfixed dye portion is readily washed off. The dyeings and prints obtained possess good lightfastness. They also have good wetfastness properties.
The present invention also provides a hydroxyl-containing or nitrogenous organic substrate, especially cellulose, polyamides and animal fibers, preferably cotton or cotton-containing substrates, dyed or printed by the above-described dyeing or printing processes.
Also claimed is the use of the compound of the formula (I) or mixtures thereof or their salts as a component in an ink-jet printing ink.
The examples hereinbelow serve to illustrate the invention.
Percentages and parts are by weight, unless otherwise stated. Temperatures are reported in degrees Celsius.